Phase formation in the ZrO(NO3)2-H3PO 4-CsF6(HF)-H2O system

Article abstract of DOI:10.1134/S0036023612060113

The phase formation in the system ZrO(NO₃)_2-H ₃PO_4-CsF(HF)-H₂O was studied at the molar ratio CsF/Zr = 1 along the sections PO^3-₄/Zr = 0.5 and 1.5 at a ZrO₂ concentration in the initial solution of 2-14 wt %. The following compounds were isolated: Cs₅Zr₄F₂₁ · 3H₂O, CsZr₂(PO₄)₃ · 2HF · 2H₂O, CsZrF₂PO₄ · H ₂O, CsZr₂F₆PO₄ · 4H ₂O (for the first time), CsHZrF₃PO₄ (for the first time), Cs_0.70ZrF(PO₄)_1.23 · nH₂O, and CsHZr₂F₂(PO₄) _2.66 · nH₂O. The compositions of CsZrF ₂PO₄ · H₂O, Cs_0.70ZrF(PO ₄)_1.23 · nH₂O, and CsHZr ₂F₂(PO₄)_2.66 · nH ₂O are conditional. All the compounds were charac-terized by crystal-optical, X-ray powder diffraction, thermal analyses, and IR spectroscopy. The formula CsHZrF₃PO₄ was established by energy-dispersive analysis with a LEO-1450 scanning electron microscope and an MS-46 CAMECA X-ray microanalyzer. Pleiades Publishing, Ltd., 2012.

Full text of DOI:10.1134/S0036023612060113

ISSN 0036ꢀ0236, Russian Journal of Inorganic Chemistry, 2012, Vol. 57, No. 7, pp. 1033–1040. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © M.M. Godneva, D.L. Motov, M.P. Rys’kina, Ya.A. Pakhomovskii, 2012, published in Zhurnal Neorganicheskoi Khimii, 2012, Vol. 57, No. 7, pp. 1107–1114.
PHYSICOCHEMICAL ANALYSIS
OF INORGANIC SYSTEMS
Phase Formation in the ZrO(NO ) –H PO –CsF(HF)–H O System
3
2
3
4
2
M. M. Godneva, D. L. Motov, M. P. Rys’kina, and Ya. A. Pakhomovskii
Tananaev Institute of Chemistry and Technology of Rare Elements and Mineral Raw Materials, Kola Research Center, Russian
Academy of Sciences, ul.Fersmana 26A, Apatity, Murmansk oblast, 184200 Russia
Received June 25, 2010
Abstract—The phase formation in the system ZrO(NO ) –H PO –CsF(HF)–H O was studied at the molar
3
2
3
4
2
3
–
ratio CsF/Zr = 1 along the sections PO4 /Zr = 0.5 and 1.5 at a ZrO2 concentration in the initial solution of
2
–14 wt %. The following compounds were isolated: Cs Zr F
⋅ 3H O, CsZr (PO ) ⋅ 2HF ⋅ 2H O,
21 2 2 4 3 2
5
4
CsZrF PO
2
⋅
H O, CsZr F PO
2
⋅
4H O (for the first time), CsHZrF PO4 (for the first time),
4
2
6
4
2
3
Cs0.70ZrF(PO )
Cs0.70ZrF(PO )
⋅
n
H O, and CsHZr F (PO )
⋅
n
H O. The compositions of CsZrF PO4 ⋅ H O,
4 1.23
2
2
2
4 2.66
2
2
2
⋅
n
H O, and CsHZr F (PO )
⋅ nH O are conditional. All the compounds were characꢀ
4 1.23
2
2
2
4 2.66 2
terized by crystalꢀoptical, Xꢀray powder diffraction, thermal analyses, and IR spectroscopy. The formula
CsHZrF PO was established by energyꢀdispersive analysis with a LEOꢀ1450 scanning electron microscope and
3
4
an MSꢀ46 CAMECA Xꢀray microanalyzer.
DOI: 10.1134/S0036023612060113
We previously studied the system ZrO(NO ) –
Table 1 presents data on the compositions of the
initial mixtures and isolated precipitates, and Fig. 1
shows a schematic of phase formation fields.
3
2
3
−
H PO –CsF–H O at the molar ratios PO Zr = 0.5
3
4
2
4
and 1.5 [1, 2]. We isolated the crystalline phases
CsZr (PO ) 2HF 2H O and CsZrF PO H O, two
3
−
⋅
⋅
⋅
2
4 3
2
2
4
2
At the molar ratio PO Zr = 0.5 (Fig. 1a) in the
4
–
modifications of CsZrF PO 0.5H O, and the amorꢀ
⋅
2
4 2
initial solution and high
F
ion content (F : Zr = 5),
3H O forms.
phous phases Cs Zr O F (PO )
⋅
3H O and the known fluorozirconate Cs Zr F
⋅
2
3
2
4
4 2
2
5
4
21
2
CsZr O F (PO ) (NO )
3
⋅
4.5H O. The compound Decreasing molar ratio F : Zr in lowꢀzirconium soluꢀ
1.25
4
4 2
3 0.5 2
tions leads to precipitation of multiphase precipitates
containing phases II and III (Table 1) and also impuꢀ
rities we failed to identify, in particular, inclusions with
Cs Zr O F (PO )
6
forms in the crystalline or glassy state, depending on
conditions. The formation of new compounds,
⋅
4 2 2
3H O was also obtained, which
3
3
1.5
refractive index < 1.470, which can be Cs ZrF6 or
2
Cs Zr O F (PO )
and Zr O (PO )
⋅
2H O, Cs Zr F (PO ) ⋅ 4.5H O,
2
3
1.5
5
4 2
2 2 3 2 4 4 2
Cs Zr F
−
⋅ 3H O, with phase III dominating. At
5
3
4
21
2
⋅
6H O, was established, which
2
3
4
4 1.33
PO Zr = 1.5, phases II, V, and VI were obtained
crystallize only in a mixture with known phases. It can
be assumed that, in the system in the presence of HF,
cesium fluorophosphatezirconates of unknown comꢀ
positions with valuable properties may form.
4
(
Fig. 1).
The Xꢀray powder diffraction pattern of phase II
differs from that of the phase CsZr (PO ) 2HF
H O isolated before [2] only in band intensity (Table 2).
⋅
⋅
2
4 3
2
The system ZrO(NO ) –H PO –CsF(HF)–H O
was studied within the molar ratio range F : Zr = 1–5
2
3
2
3
4
2
After long storage, phase II loses a part of HF; thereꢀ
fore, its HF content varies. The shape of the IR specꢀ
3
−
at the molar ratios CsF : Zr = 1 and PO Zr = 0.5 and
–1
4
trum (a broad band in the range 900–1210 cm ) sugꢀ
1
.5. HF and CsF were added while continuously stirꢀ
gests that the compound is illꢀdecrystallized (Fig. 2).
ring to ZrO(NO3)2 2H O solutions at room temperaꢀ
⋅
2
There is evidence [4] that, in the presence of H PO4
ꢀ
2
ture. After the mixtures became homogeneous, 85%
and HPO4 groups, the IR spectra of phosphates exhibit
H PO was added dropwise to them. The ZrO2 content
3
4
–1
absorption (POH) at 1210–1400 cm . However, the
δ
in solution was calculated with the consideration of
–1
presence of a band at 1210 cm is not a proof of the
existence of an HPO4 group [3]. Such a band is also
present in the spectra of a number of trisubstituted
phosphate, e.g., Na Hf(PO ) or CaZr (PO ) [4].
H PO before adding MF. After storing the obtained
3
4
mixtures for 7–45 days, precipitates were filtered off,
washed successively with water and alcohol, and dried
in air.
2
4 2
4
4 6
Because there are no other bands assigned to POH,
Identification and elemental analysis of the phases then we can believe that phase II also contains a PO4
were performed as previously [1]. group and hydrogen is bound to fluorine.
1033

1034
GODNEVA et al.
Table 1. Data on the formation of solid phases in the sections of the system ZrO(NO ) –H PO –CsF(HF)–H O
3
2
3
4
2
Precipitate composition
ZrO content F : Zr moꢀ
of initial soluꢀ lar ratio in
2
chemical composition, wt %
phase
composition
tion, wt %
additive
Cs+
F–
3−
−
Zr(IV)
H O
2
PO4
NO3
3
−
4
molar ratio PO Zr = 0.5
2
3
3
4
5
3
3
19.9
29.6
30.0
–
22.2
27.1
25.2
–
6.4
11.1
10.5
–
43.9
23.77
26.1
–
0
0
7.43
8.4
II, VIII
III, VIII
III, VIII
I
4
5
5
4
.5
0
8.2
–
0
–
1
1
24.5
25.8
30.6
28.6
17.6
16.6
3
16.1
16.2
11.2
12.8
IV
4*
0
IV
−
molar ratio PO Zr = 1.5
4
2
3
4
2
3
18.7
–
26.6
–
3.5
4.7
5.5
9.8
42.0
–
3.8
–
5.5
–
II, VIII
II, VIII
VII, VIII
V, VI
2
5
18.7
26.4
29.3
24.5
40.5
29.8
0
6.0
3.5
5
5.9
*
Initial ZrOCl2 ⋅ 8H O.
2
Phase notation: (I) Cs Zr F
⋅
3H O, (II) CsZr (PO )
⋅
2HF
⋅ 2H O, (III) CsZrF PO ⋅ H O, (IV) CsZr F PO ⋅ 4H O, (V)
2 2 4 2 2 6 4 2
4 2.66 2
5
4
21
2
2
4 3
CsHZrF PO , (VI) Cs ZrF(PO )
⋅
n
H O, (VII) CsHZr F (PO )
⋅ nH O, and (VIII) crystalline impurities of undetermined
3
4
0.70
4 1.23
2
2
2
composition.
The differential thermal analysis curve for the whereas the curve for the phase that was obtained in
phase that was isolated from HFꢀfree solutions and this work and stored for 2 years (the fluorine content of
stored for 10 months (the fluorine content of the preꢀ the precipitate is 3.1%) presents several effects (Fig. 3).
cipitate is 5.4%) shows only two endothermic events, The lowꢀtemperature endothermic effect was assigned
F/Zr
5
F/Zr
5
(
а)
(b)
I
4
3
2
4
3
2
II, VIII
III, VIII
II, VIII
V, VI
VII, VIII
6
1
0
1
0
2
4
6
2
4
ZrO , wt %
2
3
–
Fig. 1. Phase formation fields. The sections at Cs : Zr = 1 and PO4 /Zr = (a) 0.5 and (b) 1.5. The circles are experimental points.
The Roman numerals in the fields are the phase numbers.
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 57 No. 7 2012

PHASE FORMATION
1035
Table 2. Xꢀray powder diffraction data of cesium fluorophosphatezirconates
Phase
III
IV
V
VI
d
, Å
Irel
11
d
, Å
Irel
d
, Å
Irel
d
, Å
Irel
d
, Å
Irel
7
6
4
3
3
3
3
3
3
3
2
2
2
2
2
1
1
1
1
.10
7.4
98
18
62
12
15
38
81
100
70
44
28
41
12
21
23
26
16
29
60
16
30
14
31
10
17
20
7.27
6.45
4.49
3.69
3.60
3.55
3.37
3.16
3.02
2.98
2.87
2.63
2.59
2.53
2.46
2.37
2.36
2.28
2.19
2.14
2.12
2.02
2.009
1.990
1.973
1.938
22
8
1.833
1.808
1.787
1.768
1.691
1.683
1.609
1.592
1.5417
5
19
16
27
16
16
19
8
8.9
84
24
19
24
29
44
20
16
67
56
75
97
32
45
20
27
100
32
15
23
48
13
20
20
28
37
25
19
32
.0
17
7
6.2
7.2**
6.4
.56
.67
.54
.40
.31
.26
.13
.03
.70
.60
.23
.07
.04
.944
.910
.824
.604
5.75
5.25
4.50*
3.68
3.50
3.40
3.16*
2.86
2.68
2.52
2.43
2.36
2.33
2.26
2.03
1.950
1.930
32
27
61
100
67
26
13
38
26
17
13
40
5
13
19
100
10
9
5.75
5.60
5.25
4.48
4.13
11
14
6
25
3.97
3.66**
3.62
23
11
9
3.55**
3.37**
3.21
11
26
9
3.15**
3.03**
2.97**
2.87
27
27
13
21
21
5
16
15
2.78
1
1
1
1
1
1
1
.855
.840
.660
.616
.545
.515
.475
2.60**
2.53**
2.38
6
31
14
14
27
12
12
11
2.18
2.15
2.01**
1.993
1.945
1.940**
1.775
1
1
1
.912
.888
.857
Note: The data on phase V are recorded at a heating rate of 0.25 deg/min with Si as an internal standard (performed by V.Ya. Kuznetsov).
CsNO line. ** CsHZrF PO line.
*
3
3
4
to water removal, and the endothermic effect at 417–
63
was attributed to a solidꢀphase transformation ties; therefore, its composition is conditional.
5]. The latter is accompanied by a small (0.8 wt %)
Phase IV was isolated from zirconiumꢀrich soluꢀ
weight loss. The exothermic event at 657–690 is tions (Table 1), both when using ZrO(NO3)2
2H O
characteristic of an amorphousꢀtoꢀcrystalline phase and when using ZrOCl2
H O. In Fig. 1, the formaꢀ
transition, and the product of calcinations of both tion field of this phase is not indicated because it is
phases to 970
is the crystalline fluorozirconate outside of the zone covered by this figure.
CsZr (PO4)3. Although the first curve shows no exoꢀ
For CsZr F PO · 4H O anal. calcd., wt %: Cs ,
Phase III crystallizes with about 15 vol % impuriꢀ
4
°С
[
°С
⋅
2
⋅
n
2
°С
+
2
2
6
4
2
–
3–
4
thermic effect, the final calcinations product is also 22.28; Zr(IV), 30.59; F , 19.11; PO , 15.92; H O,
2
crystalline.
12.08.
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 57 No. 7 2012

1036
GODNEVA et al.
1
2
3
4
5
3
400 3000 1600 1200 800
400
, cm–1
ν
Fig. 2. IR spectra of fluorophosphatezirconates:(1) CsZr (PO ) · 2HF · 2H O, (2) CsZrF PO4 · H O, (3) CsZr F PO · 4H O,
2 4 3 2 2 2 2 6 4 2
(4)
CsHZrF PO4, and (
5
) a mixture of CsHZrF PO4 and phase VI.
3
3
+
For phase IV found, wt %: Cs , 22.9; Zr(IV), 28.3; are lamellar and form characteristic polycrystalline
–
3–
F , 17.6; PO , 15.4; H O, 12.0.
aggregates (Table 5).
4
2
The IR spectrum of phase IV in the range 1000–
100 cm exhibits a single, rather narrow, band with
–1
The IR spectrum of the crystals has no bands due to
water bending vibrations, which is indicative of the
absence of water. The spectrum presents bands
1
two maxima (Table 3; Fig. 2, curve ), which is
3
assigned to PO group and similar to the band attribꢀ
4
assigned to
γ
(POH),
ν
(PO(H)),
δ
(POH), and
ν
uted to SO group in the spectrum of the double salt
4
KZr F (H O) K SO [6]. In phase III, the PO4 group (OH), which are characteristic of HPO
group, but
2
9
2
2
2
4
4
–1
has symmetry close to Тd, i.e., is not coordinated to the shows no bands at 840–910 cm , which are inherent
zirconium.
The products of calcination of phases II, III, and
IV at 970 under the thermal analysis conditions
consist of mixtures of ZrO2 with Cs Zr (PO ) , or
−
only in the spectrum of H PO group and are absent
2
4
from the spectrum of HPO4 group [3] (Table 2). This
suggests that this compound contains a disubstituted
phosphate group. Because the substance has a thinꢀ
plate structure and is highly brittle, we failed to obtain
a polished sample for further studying the chemical
composition with an electronꢀprobe Xꢀray microanaꢀ
°С
3
1.5
4 3
Cs ZrF6 with CsZr (PO ) , or Cs Zr (PO ) with
2
2
4 3
3
1.5
4 3
CsZr (PO ) (Table 4).
2
4 3
Phase V in the acidic region contains large uniform
granular crystals in the form of monoliths, twins, and
triplets, some of which, in their turn, comprise fanꢀ lyzer. For this reason, the chemical composition of the
shaped scales (Fig. 4). Individual crystals of this phase crystals was found by energyꢀdispersive analysis with a
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 57 No. 7 2012

PHASE FORMATION
1037
Δ
T,
°
C
76
344
145
1
690
452°
С
72
417
2
657
463
701°С
537
1
44
3
6
89
83
523
9
07°С
143
622
290
334
456
45
7
50
4
5
00
7
25
1
08
513
3
16
840°С
4
30
1
44
7
47
7
89
4
3
24 350
4
40
7
14
889°
С
4
95
5
07
5
6
67
873
193
795
τ, min
Fig. 3. Differential thermal analysis curves of (
1, 2) CsZr (PO ) ⋅ 2HF ⋅ 2H O, (3) CsZrF PO4 ⋅ H O, and (4, 5) CsZr F PO ⋅
2 4 3 2 2 2 2 6 4
.
4
H O. The phases were obtained in the (1) absence or (
2
) presence of HF. The initial reactant is (
1–4) ZrO(NO3)2 nH O or
2
2
(5)
ZrOCl2
⋅
n
H O. The sample weights (
1) 0.18, (
2
) 0.17, ( ) 0.16, and ( ) 0.14 g.The heating rate is 9 deg/min.
3
,
4
5
2
LEOꢀ1450 scanning electron microscope and an MSꢀ46 phatezirconate. The average precipitate composition
CAMECA Xꢀray microanalyzer.
CsHZr F (PO ) H O
⋅
n
.
2
2
2
4 2.66
+
For CsHZrF PO anal. calcd., wt %: Cs , 35.24;
3
4
Thus, in the HFꢀcontaining and previously studied
3
−
–
Zr(IV), 24.19; F , 15.11; PO 25.18.
4
HFꢀfree systems ZrO(NO ) –H PO –CsF–H O,we
3
2
3
4
2
+
isolated cesium fluorophosphatezirconates with the
molar ratios Cs : Zr = 0.5 (CsZr (PO ) 2HF 2H O,
For phase V found, wt %: Cs , 35.3; Zr(IV), 23.9;
3
−
–
⋅
⋅
F , 13.4; PO , 24.2.
2
4 3
2
4
⋅
CsZr F PO 4H O) and 1.0 (CsZrF PO4
⋅
nH O,
2
2
6
4
2
2
Fineꢀcrystalline phase VI is plates with nearꢀisoꢀ
metric habit. For this phase found, wt %: Cs , 26.5;
+
Cs Zr
3
3
O
1.5
F
6
(PO
4
)
2
⋅
3H O, and CsHZrF PO ).
2 3 4
Moreover, in the HFꢀfree system, compounds with
Cs : Zr = 0.33 and 0.66. However, unlike fluorineꢀfree
cesium phosphatezirconates, among which there is a
compound with the molar ratio Cs : Zr = 2.0, no
3
4
−
–
Zr(IV), 26.0; F , 5.4; PO , 33.4. In comparison with
the chemical composition of phase V, the fineꢀcrystalꢀ
line phase contains noticeably less cesium and fluorine
3
−
and more PO and, according to the IR spectrum, cesium fluorophosphatezirconate with this ratio was
4
includes water. The composition of phase VI is condiꢀ isolated, although solutions at the molar ratios CsF : Zr =
.
tional and corresponds to the formula Cs ZrF(PO )
2–5 contain enough cesium. On the other hand, in
0.70
4 1.23
3
4
−
n
H O.
2
pure fluoride systems without
PO
, compounds with
the molar ratios F : Zr > 3 form, and the addition of
PO to the system prevents the formation of cesium
1.610) refractive index and the IR spectrum, this fluorophosphatezirconates with the molar ratios F : Zr >
Phase VII is isotropic, probably amorphous, forꢀ
mations constituting 85 vol %. As judged from a high
(
H
3
4
phase is a waterꢀcontaining cesium fluorophosꢀ 3. In the studied systems, the interplay between the
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 57 No. 7 2012

1038
GODNEVA et al.
–1
Table 3. Wavenumbers (cm ) at the maxima of absorption bands in the IR spectra of cesium fluorophosphatezirconates
Assignment
II
III
IV
IV*
V
VI , V
VIII, VII
[3, 4]
–
–
–
–
–
–
–
320 n
360 w st
370 w
390 v w
410 w
480
300 n
340 st
370
–
–
–
–
–
–
–
–
–
–
390
415 w
–
380
–
395 v w
405
395
–
ν(Zr–F–Zr)
–
–
ν(Zr–F)
4
60 st
–
480
–
470 st
500
460
500
–
500
–
–
500 st
–
–
–
–
–
515
530 n w
575
–
–
520
530
545
–
540
550 st
590 st
–
–
δ
as(PO4),
(Zr–F)
ν
–
560
–
6
00
40 n
–
610 w
600
–
–
610 n
680 v w
–
ν4(PO4)
6
660 w
630
–
–
630
δ
(PO4)
–
–
720
720
γ(POH)
–
–
870
–
820 b
–
–
–
–
9
40 st
–
940 n
–
940 n
1020 s
1050
1080 w st
1150
1210
1630
3080
–
–
νs(PO3)
1
000
–
1005 n
–
1010 s
1060 st
–
1
060 st w
1040 s
1040 s
1085 s
–
1060 s
1080 st
1150
1200
–
ν
as(PO3)
–
–
–
1060
–
–
–
–
1
210
630
–
–
–
1210
1620
1
1630
–
1630
–
1620
–
δ
(H–O–H)
3080 b
–
3
200 b d
3250 st d
3450 b d
–
3210
3520
3640
3200
3500
3610
ν
(O–H)
3
400 b d
3400 w d
–
3470
3580
3450
3570
3
560
*
The sample was obtained using ZrOCl2
⋅ nH O.
2
Note: b, broad; d, diffuse; n, narrow; s, strong; st, step; v s, very strong; v w, very weak; w, weak.
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 57 No. 7 2012

PHASE FORMATION
1039
Table 4. Xꢀray powder diffraction data of the products of calcination of phase IV to 970
°
C
Sample 1
Irel
Sample 2
Sample 3
d, Å Irel
d
, Å
d
, Å
Irel
d
, Å
Irel
d
, Å
Irel
4
1.907*2
1.860*1*4
1.834
9.5*3
6.70
5.05*
4.74*
4.45
1.824*4
1.790
5
4
4
4
3
3
3
3
3
3
3
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
1
1
1
.03*
24
15
70
23
10
52
36
11
7
78
43
44
100
8
58
32
16
29
13
12
19
17
14
9
13
11
11
30
23
17
35
51
27
17
14
27
22
19
16
15
20
8
16
16
21
24
26
69
12
33
24
15
88
100
39
21
83
73
43
42
11
26
23
35
32
25
80
59
21
40
53
52
25
41
32
81
31
32
20
21
27
37
16
19
30
15
38
38
17
19
14
11.6
9
10
18
41
61
15
13
28
11
100
16
92
33
53
62
26
16
14
7
17
20
11
9
63
41
19
10
5
2
3
.25*
9.40*
4.71*
4.27*
4.20*
3.88*
3.82*
3.70* *
3.64*
3.36*
3.21*
.16*2
4
3
1.750
1.700*
1.665*
1.650*
3
1.819*4
1.794*4
1.710*4
1.666*4
1.619*2*4
1.610*1*2
1.593*2
1.590*4
1.555*4
1.511*2
1.506*2
1.500*4
1.484*1*4
1.475*1
1.450*2
1.422*4
1.350*2
1.310*1
4
2
.00
.81*
2
4
3
1
4
3
4
2
.73* *
4.21*
3.82
3.70*
3.66
3.50
3.34
.65*4
.51
1.614*
4
4
4
1 4
1.600
1.590
1.574
4
.40
1
4
4
3
.18* *
4
1
.10
.99*
1.549*
2
3 4
3 4
3.17* *
3.10
1.514
1.500*4
1.477
1.453
1.420
1.360
1.327
1.296
1.270
3.15* *
2.99*2
2.85* *
2.70*3
2
.86* *
.72*1
.61*4
9
3.00
2.85*
2 4
4
14
19
8
10
23
11
11
4
3
3 4
.55*
2.72*
2.62* *
2.60* *
1
2 4
3 4
1 4
.50* * *
.44*1
2.52* *
2.49*2
2.42*1
2.35
2.26*
2.21
2.16
2.10*
2.06*
2.01
1.986
1.937
3 4
2.54* *
2.50*4
2.36
2.35
2.295*
2.22
2.195*
2.105*
2.06*3
4
.32*
1
4
.29* *
4
3
.22*
4
3
.20*
2
4
.15* *
.06*2
4
3
4
3
3
.02*
.00*
4
.970*1
.940*1
.915
2.03*
2.00*
4
3
4
2
1.856*
1.906*
16
1
2
Note: Samples 1 and 3 were obtained using ZrO(NO )
⋅
n
H O; sample 2, using ZrOCl
⋅
n
H O. Lines: (* ) Cs ZrF [7], (* )
3
2
2
2
2
3
6
3
4
CsZr (PO ) [8, card 34ꢀ0176], (* ) Cs Zr (PO ) [8, card 52ꢀ1181], and (* ) ZrO [8, card 36ꢀ420]. The semibold numbers
2
4 3
3
1.5
4 3
2
are the lines of phases of undetermined composition.
Table 5. Crystalꢀoptical characteristics of compounds
Phase
Crystal shape
Ng
Np
II
Uniform granular spherolites
1.560
1.530
III
IV
Procrystalline mass
1.562
Optically isotropic, without definite habit
1.531–1.538
1.542 ± 0.003
IV*
V
Same
Polycrystals
1.606
1.578
1.534
VI
Tabular
<1.539
1.610
VII
VIII
Without definite habit
–
1.512
1.540
1.590
*
The initial reactant is ZrOCl2
⋅ nH O.
2
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 57 No. 7 2012

1040
GODNEVA et al.
(а)
20 μm
(b)
Fig. 4. Twin crystals of the fluorophosphatezirconate CsHZrF PO4: (a) polarized light image (
×200) and (b) scanning electron
3
microscope image.
fluoride and phosphate components clearly manifests
itself.
Monoꢀ and Diphosphates (Nauka, Moscow, 1990) [in
Russian].
5
6
7
. R. G. Lepilina and N. M. Smirnova, Thermograms of
Inorganic Phosphate Compounds: Reference Book
(Nauka, Leningrad, 1984) [in Russian].
REFERENCES
. M. M. Godneva, S. D. Nikitina, D. L. Motov, V. Ya. Kuzꢀ
1
2
3
. M. M. Godneva, D. L. Motov, and M. P. Rys’kina,
Russ. J. Inorg. Chem. 56, 1363 (2011).
netsov, and O. A. Zalkind, Russ. J. Inorg. Chem. 46, 705
(2001).
. M. M. Godneva, D. L. Motov, V. Ya.Kuznetsov, and
T. E. Shchur, Russ. J. Inorg. Chem. 57, 554 (2012).
. R. L. Davidovich, T. A. Kaidalova, T. F. Levchishina,
and V. I. Sergienko, Atlas of Infrared Absorption Spectra
and Xꢀray Diffraction Data on Complex Fluorides of
Group IV and V Metals, (Nauka, Moscow, 1972) [in
Russian].
. V. V. Pechkovskii, R. Ya. Mel’nikova, E. D. Dzyuba,
et al., Atlas of Infrared Spectra of Phosphates: Orthoꢀ
phosphates (Nauka, Moscow, 1981) [in Russian].
4
. V. V. Pechkovskii, N. N. Chudinova, R. Ya.Mel’nikova,
et al., Atlas of Infrared Spectra of Phosphates: Double
8. The Powder Diffraction File (International Centre for
Diffraction Data).
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 57 No. 7 2012